Rosin modified by a phenol-ketone-formaldehyde resin



Patented Dec. 16, 1941 UNITED 'STAE Claims.

The present invention relates to synthetic resins suitable for the manufacture and more particularly to. oil=solubilized sates of a phenol, a ketone of oil varnishes condenand an aldehyde.

This application is a continuation-in-part of my applications, Ser. No.

538,248, filed May 18,

1931; Ser. No. 580,495, filed December 11, 1931; Ser. No. 594,379, filed February 20, 1932; and

Ser. No. 628,298, filed It is a general object of August 11, 1932.

the invention to proresin having normally being convertible infusible state upon heating to elevated temperatures.

More specifically, it is a high proportion of aldehyde and into the insoluble and an object of the invention to provide a resin which is characterized by the property of yielding non-penetrating varnishes, for example with linseed and Perilla oils, by which I mean the capacity to dry over porous surfaces without-penetrating the latter to any considerable extent. It is also an object of the invention to produce a resinwhich yields solu-- tions of high viscosity when mixed with equal amounts of varnolene or mineral spirits.

Resins composed of a phenol, a ketone and an aldehyde, particularly formaldehyde, are not soluble in varnish oils, especially when the proportion of formaldehyde is one of the lower members high and the phenol is of the series, but their presence in varnishes is highly desirable because of their high melting point, durability and color stability. The melting point increasing effect of the phenolic resin is increased as the proportion of formaldehyde is raised tion of formaldehyde render the thermo-setting and thus make it more but increased proporresin more easily climcult to combine the resin with rosin.

I have found that when the phenolic body, the

lretone and the formaldehyde are condensed in the presence of the rosin, presence of a compound proportions and especially in the of zinc as a catalyst,

which would yield a thermo-sletting resin with the phenolic body and the ketone; yet the mixture 'may be heated to elevated temperatures withoutv causing precipitation of phenolic resin even when the proportion of such resin is relatlvely high; Resinous products so obtained form very desirable varnishes w ith various drying and ROSIN MODIFiED BY A'IHENOL-KETONE- FORMAL!) s, PATENT orrica EHYDE RESIN Israel Rosenblum, New York, N. Y.

No Drawing. Application March 2, 1938, Serial No. 193,447

They difier from a non-drying vegetable oils.

rosin with resinous product obtained by heating a phenol-formaldehyde condensate (i. e., containing no acetone) the proportions of phenolic condensate to rosin, the molecular proportion of formaldehyde to phenol. the catalyst and the solvent, if employed, all being assumed to be the same in having a higher melting point, a higher viscosityat elevated temperatures, a'higher viscosity in 1:1 solution in varnolene and lower solubility in varnolene above the 1:1 limit: The

.point at which the modified resin is not even soluble in an equal amount of vainolene is arrived at with a lower proportion of a phenol-ketoneformaldehyde condensate than of a plienohformaldehyde condensate wherein the proportion of formaldehyde to phenol is the same.

These propertiesare contributed to a propor= tionate degree to the oil varnish made with such resins, i. e., the film is harder, the varnish is more viscous when thinned with the same amount of solvent and is more viscous when the solvent is partially'removed. sirable in, for example, wood oil. varnishes, for reasons of better drying and economy; in addition, the phenol-ketone-iormaldehyde resins are of much lower yellowing character than ordinary phenol-formaldehyde resins and in this respect compare favorably with the more expensive amyl and butyl phenol-formaldehyde resins. With linseed and Perilla oils,- as already indicated, the resins can be employed for the manufacture of so-called non-penetrating varnishes (overprint varnishes).

In carrying out the invention, the phenol is preferably first condensed with the ketone, such as acetone, to produce a diphenylol or homologous compound, which is then reacted with erably a compound of of formaldehyde may be employed the presence of rosin or equivalent acidic natural resin, and of a-catalyst prefzlnc. The proportion of formaldehyde to the phenol which is condensed with the ketone isconsiderably greater than equimolecular and may be as high as two and even thre mols of formaldehyde to one of phenol. in spite of this unusually high proportion of formaldehyde, which ordinarily would form a rapidly thermo-setting resin, the-phenol-ketoneformaldehyde in formaldehyde condensate forms a uniform prod= not with the natural resin, and this product may be combined with vegetable oils at temperatures of the order of 250-300 (3. without causing pre= clpitation of phenolic resin.

The final product may be permitted to remain acidic, in which case it may be employed for Theseproperties are dey hardening ester gum, the resulting dilution reducing the acid number; or it may be neutralized, as with glycerol. In the latter case, the glycerol is preferably added to the resinous condensate at a temperature of about 180 C., as I have found that the properties of the product are improved by beginning the esteriilcation at this relatively U tone-formaldehyde condensate is ordinarily more rapidly thermo-setting than the phenol-formaldehyde condensates which are at present combined with rosin and yet can be incorporated in at least equal amounts and even in larger amounts in rosin. In the examples described below, the weight of phenol-ketone condensate is oi the order of 8-12% of the weight of the rosin. The invention will be further described in I greater detail with the aid of the following examples, which are presented for illustrative purposes only.

. Example 1 Grams Rosin 1000 Diphenylolpropane 80 Formaldehyde (40% solution) a 160 Zinc acetate 5 (the proportion being about 3 mols of formaldehyde to each mol oi original phenol) are heated together for about 12 hours under reflux or-at 10 lbs. pressure in a closed vessel at about 110 C. The product is then dehydrated by gradually raising the temperature, the final dehydration temperature being about 180 C. At this point, an amount of glycerol equal to about 10% by weight of the rosin is added and the esterification effected by heating at about 180 C. and then raising the temperature to about 250 C. at which the mass is kept for about 12 hours. There is obtained a substantially neutral resin, the acid number being very low (about 10), the melting point, oh the other hand, being relatively high (120-125 C.). The resin has only a limited solubility in mineral spirits, but is soluble in drying and non-drying vegetable oils, and produces excellent oil varnishes therewith, which are particularly marked by their ability to dry over porous surfaces without penetrating them to any considerable extent. c

The initial reaction may take place in the presence of a solvent which is subsequently expelled.

, Example 2 To produce a resin having a higher proportion of phenol-acetone-formaldehyde condensate, it is advisable formaldehyde as follows:

Grams Rosin 1000 Diphenylolpropane 120 Formaldehyde (40% solution) 160 Zinc acetate 5 phenol originally emto reduce somewhat the proportion of are reacted as described in Example 1. After the dehydration of the resin, about 12% of glycerine based on the weight of rosin is added at about 180 C., or at a lower temperature, the temperature being gradually raised to 250 C. and the esterification being finished at such temperature. A resin is obtained having about the same melting point as in Example 1, but it is more viscous and even less soluble in mineral are heated together under reflux or at about 110 under a slight pressure. The mass is gradually heated to 250 C. without interruption and is kept at such temperature until the esteriflcation is completed. A resin similar to those obtained in Examples 1 and 2 is produced, and has the same low acid number (10-15).

The synthetic resins above described may be incorporated in varnish oils to produce nonpenetratlng varnishes in, for example, the following proportions:

Pounds Synthetic resin 100 Bodied linseed oil -r 80 Mineral spirits 75 1% cobalt naphthenate solution 3 The resin and oil ar heated to about-280 C. for about hr.; the mixture is then cooled to about 230 0., whereupon the thinner and drier are added. By reason of the presence in this varnish of a synthetic resin comprising a neutralized, rosin-modified, diphenylolpropane-formaldehyde resin, produced inthe presence, preferably, of a zinc compound catalyst, the proportion of phenolic resin being about 8 to 15% or more of the whole synthetic resin, there results a varnish which, when applied to a porous'paper surface, does not poke through," that is, does not penetrate the paper but forms' a glossy, hard film on the surfaceof the paper ("overprint). With other known types of oil-soluble, phenolic resins, a more penetrating varnish is obtained, which is undesirable for overprinting purposes.

In place of the diphenylolpropane, employed in Examples 1, 2 and 3, other condensation products of a ketone, aliphatic or aromatic, includ ing, aside from acetone, methyl butyl ketone, methyl, ethyl ketone, methyl acetone, cyclohexanone, diacetone alcohol, acetophenone, etc. with phenols, including the higher homologues of phenol and also other substituted phenols, may be employed. The rosin may be replaced in whole or in part with other natural resins of acidic character, such as dry distilled Congo resin.

It is not necessary to neutralize the rosinmodified phenolic resin substantially completely, or at all, for the resin can be mixed with a relatively large proportion of neutral ester gum and the acid number thereby reduced.

I claim:

1. The method of producing an oil-soluble phenolic resin capable of yielding non-penetrating varnishes, which comprises heating within a temperature range from refluxing temperature to a temperature of about C. a mixture consisting essentially of (1) a phenol-ketone condensation product combined in the proportion of 2 up to about mols of phenol to about 1 mol of ketone, (2) formaldehyde, and (3) rosin, the molecular proportion of the formaldehyde to original phenol being at least about 2 to 1 and the phenol-ketone product constituting from a substantial mount up to about 12% by weight of the rosin, until.a resinous condensate isobtained.

2. The method of producing an oil-soluble phenolic resin capable of yielding non-penetrating varnishes, which comprises heating within a temperature range from refluxing temperature to a temperature of about 110 C. a mixture con sisting essentially of (1) a phenol-ketone condensation product combined in the proportion of 2 mole of phenol? about 1 mol of ketone, (2) formaldehyde, and (ED-rosin. the molecular proportion of the formaldehyde to original phenol being at least about 2 to 1 and the phenol-ketone product constituting from a substantial amount 12% by weight of the romn, until a resinous condensate-is obtained, and subsedensation product combined in the proportion of 2 mols of phenol to about 1 mol of ketone, (2) formaldehyde, and (3) rosin, the molec r proportion of the formaldehyde to origin phenol being at least about 2 to 1 and the phenol-ketone product constituting from a substantial amount. up to about 12% by weight of the rosin, with a small proportion of zinc acetate, until a resinous condensate is obtained.

6. The method of producing an oil-soluble phenolic resin capable of yielding non-penetrating varnishes, which comprises heating within a temperature range from refluxing temperature to a temperature of about 110 C. a mixture consisting essentially of (1) .a phenol-ketone condensation product combined in the proportion of 2 mols of phenol to about 1 mol of ketone, (2)

' formaldehyde, and (3) rosin, the molecular proquently heating the mass with glycerol to efl'ect substantial neutralization thereof.

3. The method according to claim 1 wherein the 'phenol-ketone condensation product constitutes'about 812% by weight of the rosin.

.4. The method according to claim 1 wherein the phenol is ordinary phenol and the ketone is acetone.

5. The method of producing an oil-soluble phenolic resin capable of yielding non-penetrating varnishes, which comprises heating within a temperature range from refluxing temperature to a temperature of about 110 C. a mixture consisting essentially of (1) a phenol-ketone con- 

